Process for production of carbon tetrachloride



Patented Apr. 13, 1943 amass PROCESS FOR PRODUCTION OF CARBON TETRACHLORIDE Joy E. Beanblossom and Walton B. Scott, Niagara Falls, N. Y., assignors to Hooker Electrochemical Company, Niagara Falls, N. Y., a corporation of New York No Drawing. Application November 20, 1940, Serial No. 366,426

3 Claims.

Our process relates more particularly to production of carbon tetrachloride by chlorination of carbon disulphide.

The fundamental reaction of carbon disulphide with chlorine is as follows:

This reaction readily goes to'completion, but thereis not always a suflicient demand for the S2012 to render the process based upon the reaction commercially practicable. It is therefore necessary to find a way to return the sulphur monochloride to the process. It is also necessary to find a way to removefrom the system at some stage a quantity of sulphur equivalent to that introduced as CS2. Herein lies one of the chief difficulties in the way of production of carbon tetrachloride from carbon disulphide.

Sulphur monochloride may be considered a chlorinating agent and as such it may be reacted With more carbon disulphide. However, this re action will not ordinarily go to completion. The incomplete reaction may, for purposes of illustration, be written as follows:

Carbon disulphide boils at 46.2 C. Obviously this reaction must be conducted in such a way that the carbon disulphide will not be distilled oif. not of reaction (2) the reaction tends to reverse and the product comes off mixed with CS2, from which its separation is difficult. In the early days of the art this was not considered a serious objection, as the standard of purity for carbon tetrachloride Was then much lower than at present. Today, however, carbon tetrachloride produced by reaction (2) would be unsaleable.

Instead of chlorinating the carbon disulphide by means of elemental chlorine or sulphur monochloride, as in reactions (1) and (2), it may be chlorinated by means of sulphur dichloride. The fundamental equation of this reaction is then as follows:

This reaction readily goes to completion but here again sulphur monochloride is a by-product.

If an effort be made to diminish formation of sulphur monochloride, the reaction refuses to go to completion. A typical partial reaction of this nature is as follows:

If an attempt be made to distill off the prod-.v

tends to reverse and the product comes off contaminated with CS2.

The reaction between CS2 and S2Cl2 can, if preferred, be carried out so asto leave no unre acted S2Cl2, by using an excess of CS2, as follows:

However, the difficulty of separating the product from the CS2 and sulphur still remains. As before, if an effort be made to distill ofithe product of this reaction, more or less reversal takes place and the product coming off is contaminated by CS2.

In one of the most successful processes heretofore employed this clifficulty has been met by alternating reactions (1) and (5), distilling off a part of the product after reaction (I), transferring the by-product to reaction (5), removing all the sulphur after this reaction and recycling the residuals to reaction (1). The removal of all the elemental sulphur liberated by the reaction at each cycle involves distilling off from it the CS2 and C014 of reaction (5). As has just been shown, this results in a certain amount of reversal of the reaction. Such reversal of course means av loss of capacity in the apparatus, necessitating a greater investment than otherwise.

We have now found a way in which to accoin-. plish this same object, and one which avoids all of these fundamental difiiculties. Instead of re action (,5), we make use of reaction (2) or reaction (4) and instead of removing all the sulphur after this reaction we remove preferably only enough to balance that introduced as CS2. The remainder of the sulphur'we chlorinate to S2022. At the same time, We chlorinate any residual CS2 to CCL; and S2012, in accordance with reaction (1) or reaction (3). After this chlorination, We distill off substantially all the CCli, out of a mixture with S2012, from which CS2 is absent. We recycle the S2012 to reaction (2).

Our process is susceptible of several variations; as follows:

I. In one of its embodiments, our process involves the following sequence of reactions and steps:

(a) React CS2 with S2012 as follows:

- (5) Remove 2s, leaving 25s.

(0) Chlorinate the residuals as follows:

(d) Fractionate oif the CCL; of reaction 6 c) Return the 2S2Cl2 of reaction (6') to reac-.

chlorinating agent in the first reaction of the process. The reaction of CS2 with S012 goes a little further toward completion than that of CS2 with S2012. The steps of the process are then as follows: (a) React CS2 with S012 as follows:

(b) Remove 28, leaving 1.4S (c) C'hlorinate th residuals as follows:

(d) Fractionate off the 0014.01 reaction (7) (e) Chlorinate the S2012 of reaction (7), as follows:

(1) Return the 2S0l2 of reaction (8) to reaction (4) of the next cycle.

III. Instead of using elemental chlorine as the chlorinating agent, in the reaction constituting the third step of the process, w may use S012. The reactions and steps of the process are then as follows:

(a) React CS2 with S2012 as in I.

(12) Remove 2s, leaving ass. Chlorinate the residuals as follows:

(d) Fractionate off the 0014 of reaction (9).

(e) Return 2S2012 of reaction (9) to reaction (2) of the next cycle.

(,f) Chlorinate the remainder of the 482012 of reaction (9) as follows:

(g) Return the 4S0l2 of reaction (10) to re-; action (9) of the next cycle.

IV. Instead of using S2012 and S012 as the chlorinating agents in the reactions constituting the first and third steps of the process respectively, we may use S012 as the chlorinating agent in both of these steps. We then have the following sequence of operations:

(a) React CS2 with S012 as in II.

(b) Remove 28, leaving 1.4S. (c) Chlorinate the residuals as follows:

(d) Fractionate off the 0014 of reaction (11).

(e) Chlorinate the 282012 of reaction (11') as follows:

(f) Return 2S0l2 of reaction (10) to reaction (4) and 2S0l2 to reaction (11) of the next cycle. The crude product from each of these four variations of our process is of substantially the.

Since the 2S removed in step (b) is less than 60 per cent of the sulphur thrown out by the previous step it is a simple matter to induce this quantity of sulphur to crystallize out. The mother liquor is then drained away from it and transferred to the next step. The crystalline sulphur is necessarily quite pure, but if desired it can be further purified by remelting and heating to drive off mother liquor. This sulphur can be regarded as a lay-product and used for purposes requiring sulphur of high purity. In a balanced system, however, it would naturally be returned to the process as 0S2.

In carrying out step (c) we add the chlorinating agent more or less continuously, with agitation and refluxing, until the reaction is complete.

The separation of the 0014 from the S2012 in step (d) is a simple matter, as the former boils at 76.74" 0. and the latter at 138 0. and there is no free sulphur present during this process to cause reversal.

No technical diiiiculties are therefore involved in our process and there is no separation of 001-1 from 0S2 or distillation of 0014 out of a bath containing free sulphur.

In the foregoing illustrations of the variations in our process the reactions are to be understood as typical and we do not wish to be limited to the proportions used therein. Obviously in step (a) the proportions are susceptible of considerable variation, so long as suficient elemental sulphur is thrown out to render the removal of 2S per molecule of CS2 practicable. In step (c) it is desirable that the free sulphur be completely eliminated even though this may involve chlorinating a little beyond the end point and forming a little S012. If S012, should be formed during the chlorination, some of this will come off with the product. This will be removed by the lime purification and will represent only a slight loss of yield.

\Vhile we have in every illustration indicated the removal of sulphur equivalent to the sulphur content of the CS2, we do not wish to be limited thereto as a small quantity of by-product S2012 might be desired, in which case a correspondingly smaller quantity of sulphur would be re moved in step (b).

Although we have mentioned only S2012 and S012 as the chlorides of sulphur, we do not wish to be limited thereto as higher chlorides are known and are theoretically suitable for our process. Other compounds of sulphur and chlorine, such as sulphuryl chloride as well as chlorinating agents containing no sulphur, such as antimony pentachloride, are theoretically adaptable to our process.

We claim as our invention:

1. The process for production of carbon tetrachloride which comprises successively (a) reacting one mol of carbon disulphide with substantially two mols of sulphur dichloride until an equilibrium mixture is obtained, said mixture containing substantially all the carbon tetrachloride and elemental sulphur produced. by the reaction, together with the reagents remaining unreacted; (b) crystallizing out and removing from the mixture resulting from step (a),

including the carbon tetrachloride, elemental sulphur and residual reagents, elemental sulphur substantially equal to the sulphur content of the carbon disulphide; (c) subjecting the mixture resulting from step (b) including the carbon tetrachloride and the remainder of the elemental sulphur produced in step (a), together with the.

residual reagents, to the action of a chlorinating agent of the group consisting of elemental chlorine and sulphur dichloride, to chlorinate the carbon of the residual carbon disulphide substantially completely to carbon tetrachloride and the residual elemental sulphur as well as the sulphur of the carbon disulphide substantially completely to sulphur monochloride; (d) distilling the carbon tetrachloride away from the sulphur monochloride in the mixture resulting from step (c); and (e), chlorinating the sulphur monochloride remaining after step ((1) back to sulphur dichloride, by means of elemental chlorine, for use in a succeeding cycle of the process.

2. The process for production of carbon tetrachloride which comp-rises successively (a) reacting one mol of carbon disulphide with substantially two mols of sulphur dichloride until an equilibrium mixture is obtained, said mixture containing substantially all the carbon tetrachloride and elemental sulphur produced by the reaction, together with the reagents remaining unreacted; (b) crystallizing out and removing from the mixture resulting from step (a), including the carbon tetrachloride, sulphur and residual reagents, elemental sulphur substantially equal to the sulphur content of the carbon disulphide; (c) subjecting the mixture resulting from step (b), including the carbon tetrachloride and the remainder of the elemental sulphur produced in step (a), together with the residual reagents, to the action of elemental chlorine, to chlorinate the carbon of the residual carbon disulphide substantially completely to carbon tetrachloride and the residual elemental sulphur as well as the sulphur of the carbon disulphide substantially completely to sulphur monochloride; (d) distilling the carbon tetrachloride away from the sulphur monochloride in the mixture resulting from step (c); and (e), chlorinating the sulphur monochloride remaining after step ((2) back to sulphur dichloride, by means of elemental chlorine, for use in a succeeding cycle of the process.

3. The process for production of carbon tetrachloride which comprises successively (a) reacting one mol of carbon disulphide with substantially two mols of sulphur dichloride until an equilibrium mixture is obtained, said mixture containing substantially all the carbon tetrachloride and elemental sulphur produced by the reaction, together with the reagents remaining unreacted; (b) crystallizing out and removing from the mixture resulting from step (at), including the carbon tetrachloride, elemental sulphur and residual reagents, elemental sulphur substantially equal to the sulphur content of the carbon disulphide; (c) subjecting the mixture resulting from step (b), including the carbon tetrachloride and the remainder of the element sulphur produced in step (a), together with the residual reagents, to the action of sulphur dichloride, to chlorinate the carbon of the residual carbon disulphide substantially completely to carbon tetrachloride and the residual elemental sulphur as well as the sulphur of the carbon disulphide substantially completely to sulphur monochloride; (d) distilling the carbon tetrachloride away from the sulphur monochloride in the mixture resulting from step (c); and (e), chlorinating the sulphur monochloride remaining after step ((1) back to sulphur dichloride, by means of elemental chlorine, for use in a succeeding cycle of the process.

JOY E. BEANBLOSSOM. WALTON B. SCOTT. 

